Branched chain alkenols

ABSTRACT

Nonionic compounds in which an aluminum atom is part of an olefinically unsaturated ring system are prepared by causing interaction among aluminum, a conjugated diene and a hydrocarbon aluminum hydride in the presence of a suitable Lewis base such as 1,4-dioxane or N-methyl pyrrolidine. The resulting cyclic organoaluminum compound is useful in the synthesis of olefins and branched chain alkenols. Thus by subjecting the cyclic organoaluminum compound to hydrolysis, one or more olefins may be produced. To prepare branched chain alkenols, the cyclic organoaluminum compound is reacted with a cleavable cycloparaffinic monoether having a 3, 4 or 5 membered ring. Thereupon the reaction mixture is subjected to hydrolysis. The following novel compounds were prepared by this procedure: 1-CHLOROMETHYL-3,4-DIMETHYL-4-PENTEN-1-OL 1-CHLOROMETHYL-3,3-DIMETHYL-4-PENTEN-1-OL 2,2-BIS(CHLOROMETHYL)-4,5-DIMETHYL-5-HEXEN-1-OL 2,2-BIS(CHLOROMETHYL)-4,4-DIMETHYL-5-HEXEN-1-OL 1,5,5-TRIMETHYL-6-HEPTEN-1-OL 1,5,6-TRIMETHYL-6-HEPTEN-1-OL 4,5,6-TRIMETHYL-6-HEPTEN-1-OL 2,2,3-TRIMETHYL-5,5-BIS(CHLOROMETHYL)TETRAHYDROPYRAN

United States Patent Brendelet al.

[is] 3,692,847 [451 Sept. 19, 1972 [54] BRANCHED CHAIN ALKENOLS [72]Inventors: Gottflred J. Brendel, Baton Rouge, La. 70808; Lawrence H.Shepherd, Jr., Baton Rouge, La. 70815 [73] Assignee: Ethyl Corporation,New York,

22 Filed: Oct. 5, 1970 [21] Appl.No.: 78,213

Related U.S. Application Data [62] Division of Set. No. 77l,651, Oct.29, 1968,

Pat. No. 3,631,065.

[52] US. Cl. ..260/633, 252/522, 260/999 [51] Int. Cl ..C07c 31/34 [58]Field of Search ..260/633 [56] References Cited OTHER PUBLICATIONSShchelkunov et al., Chem. Abst. 70, 366gf, 1969 Primary Examiner-HowardT. Mars Attomey-Donald L. Johnson [57] ABSTRACT Nonionic compounds inwhich an aluminum atom is part of an olefinically unsaturated system areprepared by causing interaction among aluminum, a conjugated diene and ahydrocarbon aluminum hydride in the presence of a suitable Lewis basesuch as 1,4-dioxane or N-methyl pyrrolidine. The resulting cyclicorganoaluminum compound is useful in the synthesis of olefins andbranched chain alkenols. Thus by subjecting the cyclic organoaluminumcompound to hydrolysis, one or more olefins may be produced. To preparebranched chain alkenols, the cyclic organoaluminum compound is reactedwith a cleavable cycloparaflinic monoether having a 3, 4 or 5 memberedring. Thereupon the reaction mixture is subjected to hydrolysis. Thefollowing novel compounds were prepared by this procedure:

l-chloromethyl-3 ,4-dimethyl-4-penten- 1 -oll-chloromethyl-3,3dimethyl-4-penten-l-ol 2,2-bis( chloromethyl)-4,5-dimethyl-5-hexen- 1 -012,2-bis(chloromethyl)-4,4-dimethyl-5-hexen-l-ol1,5,5-trimethyl-6-hepten-l-ol l ,5 ,6trimethyl-6-hepten- 1 -ol 74,5,6-trimethyl-6-hepten-l-ol 2,2,3-trimethyl-5,5-

bis(chloromethyl)tetrahydropyran 2 Claims, N6 Drawings BRANCHED CHAINALKENOLS This application is a division of application Ser. No.

771,651, 'filed Oct. 29, 1968, now US. Pat. No.

where M is lithium or sodium. This adduct is insoluble in aliphatichydrocarbons and benzene. lt decomposes above 150 C. without melting.

ln copending application Ser. No. 748,613 filed July 30, 1968 one of us(GJB) has shown that aluminumcontaining reaction products are preparedby effecting reaction at an elevated temperature in asystem com: posedof aluminum, a cyclo-paraffinic monoether, a hydrocarbyl aluminumhydride and a diene. This is a complex condensation reaction whichinvolves, in part, cleavage of the ring of the ether reactant.Hydrolysis of this aluminum-containing reaction product results in theliberation of branched chain alkenols.

The present invention involves, inter alia, the discovery thatinteraction may be caused among aluminum, a conjugated diene and .ahydrocarbon aluminum hydride in the presence of certain Lewis bases toproduce novel cyclic aluminum compounds which, unlike the adducts ofLehmkuhl, are nonionic. In conducting this reaction it is important toemploy a Lewis base capable of complexing with the organoaluminumproduct without undergoing excessive cleavage. For best results thereaction is conducted in such Lewis bases as tertiary amines,dialkylethers, cycloparaffinic monoethers having a six membered ring, orcycloparaffinic diethers having a live or six membered ring.

The cyclic organoaluminum compounds produced in this process possess analuminacycloalkene moiety. For example when 2,3-dimethyl butadiene inthe diene employed in the process, the nonionic organoaluminum compoundproduced will contain the 3,4-dimethyl-aluminacyclopent-3-ene moiety:

CH: CH:

M (CHahAi CH: CH:

illustration,-when the diene reactant in butadiene or butadienesubstituted in the two position or in the two @y wawitiwe hsp n i l we?Pmdmd is m. 2 haracterizedby the formula:

wherein R is a hydrocarbon group having up to about 18 carbon atoms; Ris a hydrogen, alkyl or alkenyl group; and R" is a hydrogen or alkylgroup.

In this preferred class of Compounds R corresponds to the hydrocarbongroup initially present in the hydrocarbon aluminum hydride (mostpreferably a lower alkyl group).

On the other hand some of the product of the reaction appears to involvedisplacement of this R group and coupling of two aluminacycloalkenemoieties via an alkenylene group. In this case theproduct (whenemploying butadiene or butadiene substituted on either or both of theinternal carbon atoms) is characterized (e.g., tetrahydropyran) andcycloparaffinic diethers having a five or six membered ring (e.g.,1,4-dioxane). These complexes constitute preferred embodiments of thisinvention. Inasmuch as the cyclic aluminum compounds are nonionic, theyare soluble in conventional aliphatic and aromatic hydrocarbon solvents,such as benzene.

The cyclic aluminum compounds of this invention may be readilyhydrolyzed with water or with aqueous mineral acids or bases wherebyolefins are produced. These olefins-have the skeletal configurations ofthe hydrocarbon portion of the aluminacycloalkene moiety present in thenonionic organoaluminum compound being hydrolyzed. However the positionof the double bond in the liberated olefin is dependent to some extentupon the hydrolysis conditions employed. It is possible, for example, toproduce either alpha-olefins or olefms containing an internal doublebond.

The cyclic aluminum compounds of this invention readily cleavecycloparaffinic monoethers having three or four membered rings. Theresulting organoaluminum product on hydrolysis yields a branched chainalkeno l whose carbon content corresponds to the sum of the carbon atomsof the diene used in forming the initial cyclic aluminum compound and ofthe cycloparaffinic monoether reacted therewith.

When the cyclic aluminum compounds of this invention are in admixturewith cycloparafiinic monoethers having a five membered ring (e.g.,tetrahydrofuran) there is also a marked tendency, especially attemperatures of about 150 C. and above, for this same type ofcleavage-condensation reaction to occur. Hydrolysis of the resultingaluminum-containing intermediate results in the formation of a branchedchain alkenol having more carbon atoms than the diene from which thecyclic aluminum compound had been formed, the increase in carbon atomscorresponding to the number of carbon atoms present in the cyclicmonoether. However it is possible to maintain the nonionic cyclicaluminum compounds of this invention in contact with tetrahydrofuran andring alkylated derivatives thereof without excessive ring cleavageoccurring provided that the temperature is kept low enough.

In order to still further appreciate the practice and advantages of thisinvention reference should be had to the following illustrativeexamples.

EXAMPLE I lIsobutyl-3-methyl-aluminacyclopent-3-ene diethyl etherateActivated aluminum metal (367 m moles), diethyl ether (1.23 moles),isoprene (150 m moles) and diisobutyl aluminum hydride (24 m moles) werebrought together and heated at l45-l55 C. for three hours. Theunreacted'aluminum metal was recovered by filtration. It was therebyestablished that 62 m moles of the aluminum metal had participated inthe reaction. Hydrolysis of a portion of the liquid reaction mixturewith water followed by aqueous HCl at to 25 C. resulted in theliberation of isobutane, isopentene and a small quantity of twounsaturated C hydrocarbons. Analysis of the isolated C, hydrocarbonsindicated they had a molecular weight of 98 which corresponds to C HThis indicates that some portion of the diethyl ether was cleaved duringthe reaction and that the cleaved ether interacted with some of theisoprene or a derivative thereof thereby producing the C hydrocarbonisomers. Deuterolysis of the liquid reaction mixture liberatedisopentene, 90 percent of which was dideuterated. Material balancestudies indicated that at least 75 percent of the aluminum which hadreacted was present in the form of the 3-methylaluminacyclopent-3-enemoiety. In other words the diethyl ether was not excessively cleavedeither during the reaction or by the nonionic cyclic organoaluminumcompound produced.

Thus this reaction resulted in the formation, inter alia, of thecompound:

iitl isobutyl In a control experiment conducted under conditions similarto those described above, it was found that interaction betweendiisobutyl aluminum hydride and isoprene in diethyl ether (in theabsence of aluminum metal) did not produce any compounds which give riseto appreciable amounts of dideuterated isopentenes on deuterolysis. Mostof the isopentenes on deuterolysis of the reaction mixture weremonodeuterated.

EXAMPLE ll l-lsobutyl-3-methyl-aluminacyclopent-3 -enetetrahydropyranate isopentenes were dideuterated or 93 percent of thealu-" minum which reacted went directly to form the 3-methyl-aluminacyclopent-3-ene moiety. It was established that verylittle, if any, of the tetrahydropyran was cleaved. Thus in thisreaction the principal product formed in the reaction was:

1A1 isobutyl EXAMPLE lll l-lsobutyl-3-methyl-aluminacyclopent-3-ene N-methylpyrrolidinate N-methylpyrrolidine (1.23 moles), aluminum metal(361 m moles), isoprene m moles) and diisobutyl aluminum hydride (23 mmoles) were allowed to react at 150 C. for two hours. This resulted in36 m moles of the aluminum metal being solubilized. Deuterolysis of thereaction mixture with D,SO /D,O liberated, in addition to monodeuteratedisopentane, 61 m moles of isopentenes, 83 percent of which weredideuterated. Consequently all of the aluminum which participated in thereaction was converted to the 3-methyl-aluminacyclopent-3-ene moiety.Little or no cleavage of the cyclic amine occurred. Accordingly thisreaction resulted in the formation in good yield of the compound:

llil isobutyl EXAMPLE 1v 1-lsobutyl-3-methyl-aluminacyclopent-3-enedioxanate Reaction of aluminum metal (365 m moles), isoprene (150 mmoles), diisobutyl aluminum hydride (31 m moles) in 1,4-dioxane (1.23moles) at 150 C. for two hours resulted in solubilizing 71 m moles ofaluminum metal. Deuterolysis of the product liberated 117 m moles ofisopentenes, 107 m moles of which was dideuterated. Consequently almostall of the aluminum which entered into the reaction was converted intothe 3-methyl-aluminacyclopent-3-ene moiety. Very little, if any,cleavage of the dioxane solvent occurred.

A portion of the liquid reaction product was concentrated by vacuumremoval of some of the dioxane solvent. The nuclear magnetic resonancespectrum of the concentrated sample showed the presence of isobutylaluminum groups. This was further corroborative evidence that thereaction resulted principally in the 2 formation of the compound:

.iAl I isobutyl EXAMPLE V 1-Isobutyl-3-ethyl-aluminacyclopent-3-enedioxanate Powdered aluminum metal (365 m moles), 2-ethylbutadiene (150 mmoles), and diisobutyl aluminum hydride (30 m moles) were caused toreact in 1,4-dioxane (1.23 moles) at l45-l50 C. for two hours. A portionof the resulting liquid reaction product was subjected to hydrolysisusing water followed by aqueous HCl at 25 C. This resulted in theliberation of 3- methylpentene-l ,2-ethylbutene-l andtrans-S-methylpentene-2. The identities of these C hydrocarbons wereestablished by comparing the VPC retention times and nuclear magneticresonance spectra of these compounds with those obtained on authenticsamples of the known compounds. No cis-methylpentene-2 was detected inthe liberated mixture of C hydrocarbons. Another portion of the liquidreaction product was diluted in the dimethyl ether of diethylene glycoland the temperature of the system was reduced to 80 C. Thereupondeuterolysis was effected using NaOD/D O while allowing the system toreach room temperature. Analysis of the liberated C olefms showed thatthe mixture was composed of 50 percent trans-3-methylpentene-2, 44percent 2-ethylbutene-1, and 6 percent 3-methylpentene-1. Thetrans-3-methylpentene-2 isomer was separated from the other isomers andisolated using preparative VPC methods. Mass spectrographic analysisshowed this compound to be 95 percent dideuterated. The nuclear magneticresonance spectrum of the purified dideuterated trans-3-methylpentene-Zshowed that one deuterium atom was located in each of the cis-methylgroups:

Consequently the original reaction product contained the3-ethyl-aluminacyclopent-3-ene moiety as the compound:

A1 waist Hydrolysis or deuterolysis of other portions of the reactionproduct under differing conditions showed that it was possible to alterthe distribution of the C olefins liberated. For example hydrolysisusing dilute aqueous HCl at 05 C. yielded3 percent trans-3- EXAMPLE Vll-Isobutyl-aluminacyclopent-3-ene dioxanate When 274 m moles ofbutadiene, 365m moles aluminum metal, 1.23 moles 1,4-dioxane. and 31 mmoles diisobutyl aluminum hydride were heated for six hours at C., asolid reaction product was obtained on cooling to room temperature.Deuterolysis of a portion of the reaction mixture liberated butene-1. Acalculation indicated that hydrolysis of the entire reaction productwould have liberated 202 m moles of butene which is equivalent to 74percent of the butadiene initially added. Mass spectrographic analysisshowed the butene to be dideuterated to the extent of 97 percentindicating a good conversion of the butadiene to thealuminacyclo-pent-3-ene moiety as the compound:

In like manner, reaction among powdered aluminum,

Al WLPW Similarly. reaction at 150C. in 1,4-dioxane among aluminum,isoprene, and diethylaluminum hydride produces1-ethyl-3-methyl-auminacyclopent-S-ene:

Substitution of diphenylaluminum hydride for the diethylaluminum hydridegives rise to the production of the corresponding l-phenyl compound.

EXAMPLE VII Reaction of 1-isobutyl-3-methyl-aluminacyclopent-3- ene withtetrahydrofuran A system composed of activated aluminum powder (365 mmoles), isoprene (150 m moles), diisobutyl aluminum hydride (31 m moles)and diethyl ether (1.23 moles) was heated to 145-150 C. for two hours.The resulting diethyl ether complex ofl-isobutyl-3-methylaluminacyclopent-3-ene was separated from theunreacted aluminum metal. Excess diethyl ether was removed bydistillation and the residue dissolved in tetrahydrofuran. The resultingtetrahydrofuran solution of the cyclic aluminum compound was heated at150 C. for two hours. The reaction mixture was then subjected tohydrolysis and this resulted in the liberation of the C alkenols5,6-dimethyl-6-hepten-1-ol and 5,5-dimethyl-6-hepten-1-ol in a ratio ofapproximately 80:20, respectively. Consequently under proper reactionconditions the cyclic aluminum compounds of this invention will cleavetetrahydrofuran and make possible the preparation of branched chainalkenols (cf. Example I of Ser. No. 748,613).

EXAMPLE VIII Reaction of l-isobutyl-3-methyl-aluminacyclopent-3- enewith epichlorohydrin 1-Isobutyl-3-methyl-aluminacyclopent-3-ene wasprepared by reacting activated aluminum powder with isoprene anddiisobutyl aluminum hydride in excess 1,4-dioxane at 150 C. for twohours. The unreacted aluminum metal was removed by filtration of theliquid reaction mixture. To 43 m moles of the 1-isobutyl-3-methyl-aluminacyclopent-3-ene contained in 30 milliliters 1,4-dioxanewas slowly added 6 milliliters (78 m moles) of epichlorohydrin. Anexothermic reaction occurred. Then the reaction mixture was diluted withdiethyl ether and the mixture hydrolyzed with dilute aqueous HCl. Excessreaction solvent was removed under vacuum and the product was distilled.The main fraction boiled at 6566 C. at 1.8 mm Hg. Analysis of thisfraction by nuclear magnetic resonance and vapor phase chromatographyshowed this product to be a mixture of1-chloromethyl-3,4-dimethyl-4-penten-1-ol and1-chloromethyl-3,3-dimethyl-4-penten-l-ol, the former isomerpredominating by about 9:1

EXAMPLE IX Reaction of 1-isobutyl-3-methyl-aluminacyclopent-3- ene withbis(chloromethyl)-oxetane Another portion of the dioxane solution ofl-isobutyl-3-methyl-aluminacyclopent-3-ene of Example VIII (21 m moles)was reacted with 4.1 grams (26.5 m

moles) of bis(chloromethy1)-oxetane for three hours at C. Afterhydrolysis of the reaction product, distillation resulted in theisolation of 4.8 grams of a liquid boiling over a wide range, 60 C. at1:5 mm Hg to 134 C. at 7 mm Hg. Redistillation resulted in the isolationat 128-144 C. and 9 mm Hg of 2,2-bis(chloromethyl)-4,5-dimethyl-5-hexen-l-ol, 2,2,3-trimethyl-5,5-bis(chloromethyl)tetrahydropyran and 2,2- bis(chloromethyl)-4,4-dimethyl-5-hexen- 1 -ol.

EXAMPLE X Reaction of 1-isobutyl-3-methyl-aluminacyclopent-3- ene with2-methyl-tetrahydrofuran A dioxane solution of1-isobutyl-3-methyl-aluminacyclopent-3-ene was reacted with an excess of2- methyl-tetrahydrofuran for four hours at 150 C; After hydrolysis ofthe reaction product, it was found to contain1,5,5-trimethyl-6-hepten-1-o1, 1,5 ,6-trimethyl-6- hepten-l-ol,1,5,6-trimethyl-5-hepten-l-ol and 4,5,6- trimethyl-o-heptene-l-ol. Therelative amounts of these compounds as produced were approximately37%:49%:%:l 1%, respectively. The 5-heptene compound evidently resultedfrom isomerization of the corresponding 6-heptene compound during workup.

It will be seen from the foregoing examples that the present inventionmay be successfully applied to a wide variety of suitable reactants.Thus the diene reactant, which preferably is a conjugated dienehydrocarbon, has four to about 18 carbon atoms in the molecule, and isexemplified by such substances as butadiene, isoprene, 2,3-dimethylbutadiene, 2-ethyl butadiene, myrcene, 1,4-dimethyl butadiene,1,4-diphenyl butadiene, 2-phenyl butadiene, alpha-phellandrene, and thelike. Also the diene may be substituted by innocuous radicals as in thecase of chloroprene and 2,3- dichlorobutadiene. Dienes wherein thedouble bonds are in the terminal positions are usually most suitable.

The hydrocarbon aluminum hydride reactant used inthe process may be adihydrocarbyl aluminum hydride (R AIH) in which the R groups arehydrocarbyl groups (alkyl, aryl, cycloalkyl, alkenyl, aralkyl, alkaryl,etc.).

Thus use may be made of such compounds as dimethylaluminum hydride,diethylaluminum hydride, dipropylaluminum hydride, dibutylaluminumhydride,

diisobutylaluminum hydride, dioctylaluminum hydride,

dioctadecylaluminum hydride, diphenylaluminum hydride, ditolylaluminumhydride, dicumenylaluminum hydride, dicyclohexyl-aluminum hydride,dimethyl cyclohexyl aluminum hydride, diallylaluminum hydride,dibenzylaluminum hydride, diphenethyl-aluminum hydride and the like. Itis generally preferable to utilize a dialkylaluminum hydride, especiallythose having alkyl groups containing up to about 18 carbon atoms. Themost preferred compounds are the dialkyl aluminum hydrides in which eachalkyl group is a lower alkyl group and thus contains up to about sixcarbon atoms. If desired, the hydrocarbon aluminum hydride may begenerated in situ by initially reacting aluminum with trihydrocarbylaluminum (e.g. triethylaluminum) under a hydrogen atmosphere accordingto known technology.

The aluminum used in the process of this invention may be in the form ofchips, turnings, powder, or other similar particulated states. It isdefinitely preferable to employ activated aluminum. Methods forproducing activated aluminum are standard and well known in the art. Forfurther details, reference may be had, for example, to U.S. Pat. .Nos.2,885,314; 2,892,738; 2,921,876; 3,100,786 and 3,104,252.

As. noted above, reaction is conducted in the presence of a Lewis basehaving suitable chemical stability under the reaction conditions beingutilized. In most cases this Lewis base will be employed as theprincipal reaction solvent--i.e., the reaction will be conducted in theLewis base selected for use. However if desired the reaction may beeffected in a suitable inert hydrocarbon medium (e.g., paraffinic oraromatic hydrocarbon solvents such as hexane, heptane, octane, decane,cyclohexane, benzene, toluene, xylenes, and the like) provided asuitable amount of the Lewis base is also present in the reactionsystem. Ordinarily the system should contain at least 1-2 mols of Lewisbase per mol of diene employed. Particularly convenient Lewis bases foruse in the process are tertiary amines (e.g., trimethyl amine,dimethyl-ethyl amine, triethyl amine, tributyl amine, triphenyl amine,tribenzyl amine, benzyldimethyl amine, N-methyl morpholine, N,N-diethylaniline, N,N,N,N'-tetramethyl methylene diamine, N,N,N,N'-tetramethylethylene diamine, pyridine, N-methyl pyrrolidine, triethylene diamine,quinuclidine, and the like); dialkyl ethers (e.g., dimethyl ether,diethyl ether, diisopropyl ether, methylisoamyl ether, dibutyl ether,dihexyl ether and the like); cycloparaffinic monoethers having a sixmembered ring (e.g., tetrahydropyran--pentamethylene oxide--and ringalkylated derivatives thereof); and cycloparaffinic diethers having afive or six membered ring (e.g., 1,4-dioxane, 1,3-dioxolane, 2-methyl-2-ethyl-l,3-dioxolane; and the like); and other similarsubstances which tend not to be excessively cleaved in the reaction,such as dicyclohexyl ether, dibenzyl ether, and the like. The relativeproportions of the reactants and reaction diluentsdo not appear to becritical as long as there is present a sufficient amount of eachreactant to participate in the reaction.

In conducting the process for forming the cyclic organoaluminumcompounds of this invention, elevated temperatures are employed.Generally, temperatures within the range of about 100 C. to about 180 C.will be found satisfactory, temperatures within the range of about toabout C. being preferred.

Ordinarily the reaction will be conducted at atmospheric pressure or atthe ambient pressures encountered when conducting the reaction in aclosed reaction vessel. However when using some of the lower boilingLewis base solvents, e.g., dimethyl ether, trimethyl amine or the like,it is desirable to conduct the reaction at a high enough pressure tokeep the system in the liquid state of aggregation. Thus pressures up toabout 50 atmospheres may be employed.

It will of course be understood that the reaction mix ture should bekept essentially anhydrous and that exposure of the reaction system toair should be kept at a minimum.

The period of time during which the reactants interact with each otheris susceptible to considerable variation and is generally discretionary.In general, the higher the reaction temperature, the shorter the.reaction or contact time.

The procedures of above Examples VIII-X, inclusive, gave rise to theproduction of novel compounds, one a cyclic ether and the remainder agroup of alkenols. All of these compounds have special fragrancecharacteristics and thus are of utility as perfumes, especially inconnection with household detergents, shampoos, toilet bars and thelike. The alkenols are of particular utility as chemical intermediatesinasmuch as they have an olefinic double bond near one end of themolecule and a hydroxyl group at or near the other end. Thus either orboth of these reaction sites may be @2 3 UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION Patent No. 5, 9 1 Dated September 9, 97

Inventor(s) Gottfried J. Brendel and Lawrence H. Shepherd, Jr.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 1, line 50, "in the should read is the --5 line 55 in theformula) "C C should read C 2 CV line 67, "reactant in" should readreactant is Column 2, line (in the formula) "C C" should read C C -5line 26 in the formula; "C C" should read C C --3 line 59 in the formulaC C should read C I C Column 8, line 21, trimethy1-6--heptene-l-ol"should read trimethyl-6-he ten-l-ol line 24, 57%=49%=%;11%" should read57%:49% 3%:ll%

Signed and sealed this 13th day of February 1973.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents

2. 2,2-Bis(chloromethyl)-4,5-dimethyl-5-hexen-1-ol.